[0001] The present invention relates to a method in which waste plastic material or waste
rubber material is recycled so as to obtain hydrocarbon oil and an apparatus used
for carrying out the method.
[0002] In present motor vehicles, a vehicle body panel, various interior parts, tires, etc.
are formed by polymer such as plastic material or rubber material and ratio of plastic
material or rubber material used for each motor vehicle has been raised gradually.
Therefore, even if only one motor vehicle is scrapped after its service life, a considerable
quantity of waste plastic material or waste rubber material is generated. Since a
number of motor vehicles are scrapped every day at present, a total quantity of waste
plastic material or waste rubber material is enormous.
[0003] Such waste plastic material or waste rubber material, which is produced in huge quantity
only in connection with motor vehicles, is tested for various effective recycling
purposes in various industrial fields including car industry. Furthermore, efforts
for further promoting the recycling are being exerted. Under these circumstances,
Japanese Patent Laid-Open Publication No. 63-178195 (1988) proposes, as one example
of recycling of waste plastic material or waste rubber material, that hydrocarbon
oil is produced from waste plastic material or waste rubber material and the produced
hydrocarbon oil is used as fuel, etc.
[0004] In a known method of producing hydrocarbon oil from waste plastic material, the waste
plastic material is subjected to thermal cracking so as to obtain thermal cracking
gas and the thermal cracking gas is subjected to vapor phase catalytic cracking by
using proper catalyst so as to obtain catalytic cracking gas and then, the catalytic
cracking gas is cooled so as to obtain hydrocarbon oil having relatively low boiling
point. For example, in a method disclosed in the above mentioned prior art document
No. 63-178195 (1988), thermal cracking of the plastic material is performed in melt
phase at a temperature of 390 °C to 500 °C, while vapor phase catalytic cracking of
the thermal cracking gas is performed at a temperature of 200 °C to 350 °C by using
zeolite as the catalyst. As a result, low-boiling hydrocarbon oil containing 22 carbon
atoms or less is obtained. This known method in which the hydrocarbon oil is obtained
by thermal cracking, vapor phase catalytic cracking and cooling steps can be applied
to not only waste plastic material but waste rubber material.
[0005] Meanwhile, in case thermal cracking of waste plastic material is performed at relatively
high temperature, ratio of gaseous component increases and thus, recovery of desired
low-boiling hydrocarbon oil drops. A countermeasure for eliminating this drawback
is proposed in, for example, Japanese Patent Laid-Open Publication No. 52-144088 (1977)
in which in order to set thermal cracking temperature relatively low, thermal cracking
of the waste plastic material is performed in a state where mixture of the waste plastic
material and aluminum chloride acting as catalyst is being stirred.
[0006] When the hydrocarbon oil is produced from waste plastic material or waste rubber
material as described above, catalyst such as zeolite used for vapor phase catalytic
cracking of the thermal cracking gas produced through thermal cracking of the waste
plastic material or the waste rubber material is maintained at not more than a predetermined
temperature lower than a temperature for thermal cracking of the waste plastic material
or the waste rubber material so as to prevent a phenomenon in which heat deterioration
of the catalyst leads to, for example, production of a large quantity of hydrocarbon
gas. Therefore, the thermal cracking gas produced through thermal cracking of the
waste plastic material or the waste rubber material is cooled by the catalyst during
vapor phase catalytic cracking. Consequently, such a problem arises that heavy component
(wax component) contained in the thermal cracking gas adheres to the catalyst, thereby
resulting in drop of function of the catalyst. Meanwhile, the heavy component contained
in the thermal cracking gas subjected to vapor phase catalytic cracking is mixed into
the hydrocarbon oil obtained by vapor phase catalytic cracking, thereby undesirably
resulting in deterioration of quality and drop of recovery of the finally recovered
hydrocarbon oil.
[0007] Furthermore, when in order to set thermal cracking temperature relatively low, thermal
cracking of the waste plastic material is performed in a state where mixture of the
waste plastic material and aluminum chloride acting as catalyst is being stirred as
described above, molten substance obtained by thermal cracking has relatively high
viscosity and thus, such disadvantages are incurred that efficiency for stirring the
mixture is not so high and the catalyst evaporates rapidly.
[0008] Accordingly, an essential object of the present invention is to provide a method
of obtaining hydrocarbon oil from waste plastic material or waster rubber material
and an apparatus used for carrying out the method, with a view to eliminating the
above mentioned disadvantages inherent in prior art that when the hydrocarbon oil
is produced based on thermal cracking gas obtained by thermal cracking of the waste
plastic material or the waste rubber material, function of catalyst used for vapor
phase catalytic cracking of the thermal cracking gas drops and that when thermal cracking
of the waste plastic material is performed at relatively low temperature in a state
where mixture of the waste plastic material and catalyst is being stirred, efficiency
for stirring the mixture is not so high and the catalyst evaporates rapidly, in which
content of heavy component of the finally recovered hydrocarbon oil is reduced and
yield of the hydrocarbon oil is raised as compared with a case where the thermal cracking
gas is subjected to vapor phase catalytic cracking by using zeolite or the like as
the catalyst.
[0009] In order to accomplish this object of the present invention, a method of obtaining
hydrocarbon oil from waste plastic material or waste rubber material, according to
the present invention comprises the steps of: subjecting the waste plastic material
or the waste rubber material to thermal cracking so as to obtain a thermal cracking
product; liquefying the thermal cracking product into a liquefied product; causing
a liquid phase cracking reaction of the liquefied product under action of a catalyst
on the liquefied product so as to produce a cracking product; and cooling the cracking
product so as to obtain the hydrocarbon oil.
[0010] In the method, it is preferable that the catalyst used for the liquefied product
is acid catalyst.
[0011] Meanwhile, an apparatus for producing hydrocarbon oil, according to the present invention
comprises: a thermal cracking portion in which waste plastic material or waste rubber
material is subjected to thermal cracking at a predetermined temperature so as to
obtain a thermal cracking product; a liquefaction portion in which the thermal cracking
product is liquefied so as to obtain a liquefied product; a liquid phase cracking
portion in which a liquid phase cracking reaction of the liquefied product is caused
under action of a catalyst on the liquefied product so as to obtain a cracking product
of the liquefied product; and an oil recovery portion in which the hydrocarbon oil
is produced from the cracking product.
[0012] In the apparatus, it is preferable that acid catalyst is used as the catalyst for
the liquefied product in the liquid phase cracking portion.
[0013] As described above, in the method of obtaining the hydrocarbon oil from the waste
plastic material or the waste rubber material, according to the present invention
and the hydrocarbon oil producing apparatus of the present invention, the waste plastic
material or the waste rubber material is subjected to thermal cracking so as to obtain
the thermal cracking product. Subsequently, without being subjected to vapor phase
catalytic cracking employing catalyst, the thermal cracking product is liquefied and
then, the liquid phase cracking reaction of the liquefied product is caused by using
the catalyst such as acid catalyst so as to produce the cracking product such that
the hydrocarbon oil is obtained from the cracking product.
[0014] Therefore, in accordance with the present invention, such problems are eliminated
that when catalyst is used for vapor phase catalytic cracking of thermal cracking
gas obtained, as thermal cracking product, by thermal cracking of waste plastic material
or waste rubber material, heavy component contained in the thermal cracking gas adheres
to the catalyst so as to deteriorate function of the catalyst and that when thermal
cracking of the waste plastic material is performed at relatively low temperature
in a state where mixture of the waste plastic material and catalyst is being stirred,
efficiency for stirring the mixture is not so high and the catalyst evaporates rapidly.
[0015] Furthermore, in accordance with the present invention, since content of heavy component
of the finally recovered hydrocarbon oil is reduced and yield of the hydrocarbon oil
is raised as compared with a case where the thermal cracking gas is subjected to vapor
phase catalytic cracking by using zeolite or the like as the catalyst, quality and
recovery of the hydrocarbon oil are improved.
[0016] This object and features of the present invention will become apparent from the following
description taken in conjunction with the preferred embodiment thereof with reference
to the accompanying drawings, in which:
Fig. 1 is a schematic view of a hydrocarbon oil producing apparatus of the present
invention, which is used for carrying out a method of obtaining hydrocarbon oil from
waste plastic material or waste rubber material, according to the present invention;
and
Fig. 2 is a schematic view of an experimental apparatus employed for comparison between
the method of the present invention and another method.
[0017] Referring now to the drawings, there is shown in Fig. 1, a hydrocarbon oil producing
apparatus K of the present invention, which is used for carrying out a method of obtaining
hydrocarbon oil from waste plastic material or waste rubber material, according to
the present invention. In Fig. 1, the apparatus K includes a hopper 12 having a feeder,
in which recycling material 11 such as waste plastic material including ground high-density
polyethylene (HDPE) or waste rubber material is stored. A thermal cracking tank 13
for performing thermal cracking of the recycling material 11 is provided in operative
association with the hopper 12. The thermal cracking tank 13 includes a tank body
14 to which the recycling material 11 is supplied from the hopper 12 through the feeder
and a heater 15 for heating the tank body 14 so as to perform thermal cracking of
the recycling material 11 supplied into the tank body 14. The heater 15 is provided
outside the tank body 14. A temperature sensor (not shown) for detecting temperature
of interior of the tank body 14 is provided on the tank body 14. Temperature control
of the heater 15 is performed on the basis of detection output of this temperature
sensor such that thermal cracking temperature in the tank body 14 ranges from 450
°C to 550 °C.
[0018] Thermal cracking gas is obtained as thermal cracking product in the tank body 14.
An upper portion of the tank body 14 of the thermal cracking tank 13 is coupled with
one end of a duct 17 for guiding the thermal cracking gas to a liquefaction portion
16. The other end of the duct 17 is coupled with a duct 18 provided with the liquefaction
portion 16. A temperature sensor 19 for detecting temperature of light component gas
flowing upwardly out of the liquefaction portion 16 is provided at an upper end of
the duct 18 so as to be disposed above the liquefaction portion 16.
[0019] A lower end of the duct 18 is coupled with a catalytic reaction tank 20. The catalytic
reaction tank 20 is provided with a rotary stirrer 21, a liquid quantity sensor 22
and a catalyst feeder 23. The catalyst feeder 23 stores acid catalyst 24 such as synthetic
zeolite used as builder for synthetic detergent, etc. and sulfuric acid so as to supply
the acid catalyst 24 into the catalytic reaction tank 20. A temperature sensor (not
shown) for detecting temperature of interior of the catalytic reaction tank 20 is
provided on the catalytic reaction tank 20. Temperature control of a heater 25 for
heating the catalytic reaction tank 20 is performed on the basis of detection output
of this temperature sensor such that temperature in the catalytic reaction tank 20
ranges from 200 °C to 350 °C.
[0020] One end of a duct 31 provided with a cooler 30 is coupled with the upper end of the
duct 18, at which the temperature sensor 19 is disposed. The other end of the duct
31 extends into a neutralization and oil separation tank 32. The neutralization and
oil separation tank 32 stores 20 % sodium hydroxide aqueous solution 33 acting as
neutralization liquid and the other end of the duct 31 is dipped into the 20 % sodium
hydroxide aqueous solution 33. An upper portion of the neutralization and oil separation
tank 32 is communicated with exterior through a duct 34.
[0021] Hereinbelow, one example of the method of obtaining hydrocarbon oil from waste plastic
material or waste rubber material by using the hydrocarbon oil producing apparatus
K of the above described arrangement, according to the present invention is described.
Initially, the recycling material 11 stored in the hopper 12 is supplied into the
tank body 14 of the thermal cracking tank 13 by the feeder provided on the hopper
12. Then, the tank body 14 is heated by the heater 15 of the thermal cracking tank
13 such that thermal cracking of the recycling material 11 is performed in the tank
body 14. At this time, temperature control of the heater 15 is performed such that
thermal cracking temperature in the tank body 14 ranges from 450 °C to 550 °C. As
a result, thermal cracking gas which is thermal cracking product obtained by thermal
cracking of the recycling material 11 is obtained in the tank body 14.
[0022] The thermal cracking gas obtained in the tank body 14 is drawn, through the duct
17 and a portion of the duct 18, into the liquefaction portion 16. In the liquefaction
portion 16, heavy component in the thermal cracking gas is liquefied. Then, the heavy
component liquefied by the liquefaction portion 16 is carried, as liquefied product
35, into the catalytic reaction tank 20 via the duct 18.
[0023] When the liquid quantity sensor 22 detects that the liquefied product 35 in the catalytic
reaction tank 20 has reached a predetermined quantity, a detection output signal is
delivered by the liquid quantity sensor 22. In response to this detection output signal
from the liquid quantity sensor 22, a proper quantity of the acid catalyst 24 is supplied
from the catalyst feeder 23 into the catalytic reaction tank 20. Furthermore, in response
to the detection output signal from the liquid quantity sensor 22, not only the rotary
stirrer 21 is actuated but the catalytic reaction tank 20 is heated by the heater
25 such that temperature in the catalytic reaction tank 20 ranges from 200 °C to 350
°C.
[0024] In the catalytic reaction tank 20, the liquefied product 35 to which the acid catalyst
24 is added causes a liquid phase cracking reaction under action of the acid catalyst
24 while being stirred by the rotary stirrer 21 and being heated to a temperature
of 200 °C to 350 °C. Thus, in the catalytic reaction tank 20, catalytic reaction cracking
gas is obtained as cracking product. The catalytic reaction cracking gas obtained
in the catalytic reaction tank 20 is drawn to the liquefaction portion 16 through
the duct 18. Thus, heavy component contained in the catalytic reaction cracking gas
from the catalytic reaction tank 20 is liquefied in the liquefaction portion 16 so
as to be again returned to the catalytic reaction tank 20 by way of the duct 18.
[0025] Thus, light component gas contained in the catalytic reaction cracking gas obtained
in the catalytic reaction tank 20 passes through the liquefaction portion 16 via the
duct 18 and flows to the upper end of the duct 18, which is disposed above the liquefaction
portion 16. At this time, temperature control in the liquefaction portion 16 is performed
on the basis of detection output from the temperature sensor 19 such that the light
component gas flowing from the liquefaction portion 16 to the upper end of the duct
18 ranges from 200 °C to 250 °C. Thereafter, the light component gas flowing from
the liquefaction portion 16 to the upper end of the duct 18 is fed from the upper
end of the duct 18 to the cooler 30 through the duct 31. Thus, the light component
gas is liquefied into low-boiling hydrocarbon oil by the cooler 30 and the low-boiling
hydrocarbon oil is supplied, via a portion of the duct 31 downstream of the cooler
30, into the 20 % sodium hydroxide aqueous solution 33 stored, as neutralization liquid,
in the neutralization and oil separation tank 32.
[0026] Therefore, in the neutralization and oil separation tank 32, first and second low-boiling
hydrocarbon oils are, respectively, obtained by cooling by the cooler 30 light component
gas contained in the thermal cracking gas from interior of the tank body 14 and light
component gas contained in the catalytic reaction cracking gas obtained in the catalytic
reaction tank 20. Hydrochloric acid mixed into the first and second low-boiling hydrocarbon
oils is neutralized by the 20 % sodium hydroxide aqueous solution 33 acting as neutralization
liquid. Thus, in the neutralization and oil separation tank 32, a layer of the 20
% sodium chloride aqueous solution 33, a layer of low-boiling hydrocarbon oil 36 and
a layer of gas component 37 are formed sequentially upwardly in this order from a
bottom of the neutralization and oil separation tank 32. Namely, in the neutralization
and oil separation tank 32, the low-boiling hydrocarbon oil 36 produced by thermal
cracking of the recycling material 11 is recovered. Meanwhile, the gas component 37
obtained in the neutralization and oil separation tank 32 is recovered through the
duct 34 so as to be utilized at, for example, the heaters 15 and 25.
[0027] As described above, when the low-boiling hydrocarbon oil 37 is recovered from the
thermal cracking gas obtained by thermal cracking of the recycling material 11, the
thermal cracking gas obtained by thermal cracking of the recycling material 11 is
not subjected to vapor phase catalytic cracking employing catalyst but is liquefied
into the liquefied product 35 in the liquefaction portion 16. Then, in the catalytic
reaction tank 20, the liquefied product 35 causes a liquid phase cracking reaction
by using, for example, synthetic zeolite as the acid catalyst so as to produce the
catalytic reaction cracking gas such that the low-boiling hydrocarbon oil 36 is obtained
by cooling the catalytic reaction cracking gas.
[0028] Therefore, in accordance with the present invention, such problems are eliminated
that when catalyst is used for vapor phase catalytic cracking of the thermal cracking
gas obtained by thermal cracking of the waste plastic material, heavy component contained
in the thermal cracking gas adheres to the catalyst so as to deteriorate function
of the catalyst and that when thermal cracking of the waste plastic material is performed
at relatively low temperature in a state where mixture of the waste plastic material
and catalyst is being stirred, efficiency for stirring the mixture is not so high
and the catalyst evaporates rapidly.
[0029] Furthermore, in accordance with the present invention, content of heavy component
of the low-boiling hydrocarbon oil 36 recovered in the neutralization and oil separation
tank 32 is low and yield of the low-boiling hydrocarbon oil 36 is raised as compared
with a case where the thermal cracking gas is subjected to vapor phase catalytic cracking
by using zeolite or the like as the catalyst.
[0030] By using an experimental apparatus shown in Fig. 2, experiments were conducted by
the present inventors for comparison between recovery of hydrocarbon oil obtained
from waste plastic material in the method of the present invention and that obtained
from waste plastic material in another method other than the method of the present
invention. In Fig. 2, the experimental apparatus includes an annular oven 40 in which
a closed-end thermal cracking tube 41 made of stainless steel is placed on a heat
insulator 42 so as to be surrounded by an annular heater 40A. A mouth 41A disposed
at an upper end of the closed-end thermal cracking tube 41 is closed by a plug 43.
One end of a duct 45 is coupled with a through-hole 41B formed at an upper portion
of the closed-end thermal cracking tube 41.
[0031] A flask 46 has projecting mouths 46A, 46B and 46C. A plug 47 is provided at the projecting
mouth 46A of the flask 46, while the projecting mouth 46B of the flask 46 is closed
by a plug 52. The other end of the duct 45 pierces through the plug 47 into the projecting
mouth 46A. The flask 46 is provided in an oil tank 49 placed on a magnetic stirring
machine 48 and a heater 50 is provided in the oil tank 49. A stirrer 51 which is remotely
driven by the magnetic stirring machine 48 is provided in the flask 46. One end of
a duct 53A of a cooler 53 is coupled with the projecting mouth 46C of the flask 46.
A plug 55 is provided at a mouth of a neutralization and oil separation bottle 54.
The other end of the duct 53A of the cooler 53 pierces through the plug 55 of the
neutralization and oil separation bottle 54 into the neutralization and oil separation
tank 54. Meanwhile, 20 % sodium hydroxide aqueous solution 56 acting as neutralization
liquid is stored in the neutralization and oil separation tank 54 such that the other
end of the duct 53A of the cooler 53 reaches the 20 % sodium hydroxide aqueous solution
56. Furthermore, interior of the neutralization and oil separation bottle 54 is communicated
with exterior via a duct 57 piercing through the plug 55.
[0032] In a first experiment employing such experimental apparatus, hydrocarbon oil is produced
from waste plastic material in the method of the present invention. Initially, 5 g
of high-density polyethylene 60 is put, as waste plastic material, into the closed-end
thermal cracking tube 41 from the mouth 41A. Subsequently, the mouth 41A of the closed-end
thermal cracking tube 41 is closed by the plug 43. Meanwhile, 1 g of synthetic zeolite
used as builder for synthetic detergent is poured, as catalyst 61, into the flask
46 from the projecting mouth 46B. Then, the projecting mouth 46B of the flask 46 is
closed by the plug 52. Thereafter, the flask 46 is heated by the heater 50 provided
in the oil tank 49 such that interior of the flask 46 is maintained at a temperature
of about 200 °C. While the stirrer 51 in the flask 46 is being remotely driven by
the magnetic stirring machine 48, the annular oven 40 is heated by the annular heater
40A in the annular oven 40 such that interior of the annular oven 40 is maintained
at a temperature of 450 °C.
[0033] As a result, in the closed-end thermal cracking tube 41, 5 g of the high-density
polyethylene 60 is subjected to thermal cracking into thermal cracking gas. When the
thermal cracking gas is delivered into the flask 46 from interior of the closed-end
thermal cracking tube 41 via the duct 45, the thermal cracking gas is cooled in the
duct 45 and the flask 46 so as to be liquefied into liquefied product 62 such that
the liquefied product 62 remains in the flask 46. Through stirring effected by the
stirrer 51, the liquefied product 62 in the flask 46 is mixed with the catalyst 61
formed by 1 g of synthetic zeolite used as builder for synthetic detergent so as to
cause a liquid phase cracking reaction by action of the catalyst 61. Thus, cracking
gas produced by the liquid phase cracking reaction of the liquefied product 62 is
obtained in the flask 46 so as to be led to the duct 53A of the cooler 53. Therefore,
the cracking gas from the flask 46 is cooled into low-boiling hydrocarbon oil by the
cooler 53. The low-boiling hydrocarbon oil is further collected into the neutralization
and oil separation bottle 54 via the duct 53A of the cooler 53. As a result, in the
neutralization and oil separation bottle 54, a layer of 20 % sodium hydroxide aqueous
solution 56, a layer of low-boiling hydrocarbon oil 63 and a layer of unreactive cracking
gas component 64 are formed sequentially upwardly in this order from a bottom of the
neutralization and oil separation bottle 54.
[0034] When the unreactive cracking gas component 64 obtained in the neutralization and
oil separation bottle 54 as described above is recovered through the duct 57 and the
low-boiling hydrocarbon oil 63 recovered in the neutralization and oil separation
bottle 54 is discharged, production of no heavy component (wax component) is found.
Meanwhile, a ratio by weight of the discharged low-boiling hydrocarbon oil 63 to the
recovered unreactive cracking gas component 64 is 57 : 43.
[0035] On the other hand, in a second experiment employing the above experimental apparatus
for comparison with the first experiment, hydrocarbon oil is produced from waste plastic
material in another method other than the method of the present invention. In this
method, waste plastic material is subjected to thermal cracking into thermal cracking
gas and the thermal cracking gas is subjected to vapor phase catalytic cracking into
catalytic cracking gas by using proper solid acid catalyst. Then, the catalytic cracking
gas is cooled and neutralized so as to obtain low-boiling hydrocarbon oil. To this
end, 5 g of high-density polyethylene acting as waste plastic material is prepared
so as to be subjected, for 1 g of the high-density polyethylene at a time, to thermal
cracking a total of five times, 3g of zeolite is used as solid acid catalyst for vapor
phase catalytic cracking and temperature is set at 250 °C. As a result, unreactive
cracking gas, low-boiling hydrocarbon oil and heavy component (wax component) are
obtained finally and a ratio by weight of the low-boiling hydrocarbon oil to the heavy
component and the unreactive cracking gas is 42 : 1 : 57.
[0036] It is found from the above mentioned results of the first and second experiments
that recovery of the hydrocarbon oil produced from waste plastic material in the method
of the present invention is remarkably improved in comparison with that produced from
waste plastic material in another method other than the method of the present invention.
[0037] As is clear from the foregoing description of the method of obtaining the hydrocarbon
oil from the waste plastic material or the waste rubber material, according to the
present invention and the hydrocarbon oil producing apparatus of the present invention,
the waste plastic material or the waste rubber material is subjected to thermal cracking
into the thermal cracking product. Subsequently, without being subjected to vapor
phase catalytic cracking employing catalyst, the thermal cracking product is liquefied
and then, causes a liquid phase cracking reaction by using the acid catalyst as catalyst
so as to produce the cracking product such that the hydrocarbon oil is obtained from
the cracking product.
[0038] Therefore, in accordance with the invention, such problems are eliminated that when
catalyst is used for vapor phase catalytic cracking of the thermal cracking gas obtained,
as the thermal cracking product, by thermal cracking of the waste plastic material
or the waste rubber material, heavy component contained in the thermal cracking gas
adheres to the catalyst so as to deteriorate function of the catalyst and that when
thermal cracking of the waste plastic material is performed at relatively low temperature
in a state where mixture of the waste plastic material and catalyst is being stirred,
efficiency for stirring the mixture is not so high and the catalyst evaporates rapidly.
[0039] Furthermore, in accordance with the present invention, since content of heavy component
of the finally recovered hydrocarbon oil is reduced and yield of the hydrocarbon oil
is raised as compared with a case where the thermal cracking gas is subjected to vapor
phase catalytic cracking by using zeolite or the like as the catalyst, quality and
recovery of the hydrocarbon oil are improved.